CN109306180A - A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film - Google Patents

A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film Download PDF

Info

Publication number
CN109306180A
CN109306180A CN201811145199.1A CN201811145199A CN109306180A CN 109306180 A CN109306180 A CN 109306180A CN 201811145199 A CN201811145199 A CN 201811145199A CN 109306180 A CN109306180 A CN 109306180A
Authority
CN
China
Prior art keywords
polymer resin
aromatic heterocyclic
heterocyclic polymer
high transparency
fluorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201811145199.1A
Other languages
Chinese (zh)
Inventor
王庭辉
刘文熙
潘鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201811145199.1A priority Critical patent/CN109306180A/en
Publication of CN109306180A publication Critical patent/CN109306180A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to resin technology fields, aromatic heterocyclic polymer resin more particularly to a kind of high transparency and preparation method thereof and application in fiber or film, the aromatic heterocyclic polymer resin the preparation method comprises the following steps: using at least one of fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid and hydrazine sulfate as reaction raw materials, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Aromatic heterocyclic polymer resin transparency with higher of the invention also has the performances such as good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent, excellent combination property.

Description

A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and in fiber or thin The application of film
Technical field
The present invention relates to resin technology fields, and in particular to a kind of aromatic heterocyclic polymer resin of high transparency and its preparation side Method and application in fiber or film.
Background technique
In heterocyclic compound cyclic organic compounds, constitute there are also other atomic time outside the atom carbon atom of ring, it is this kind of Cyclic organic compounds are called heterocyclic compound, and non-carbon is known as hetero atom.The most common hetero atom is oxygen and sulphur, on heterocycle Can have a hetero atom, can also there are two or more hetero atom, hetero atom can be a kind of atom, be also possible to two kinds Different atoms.As cycloalkane, heterocycle can also be divided into alicyclic heterocyclic and heteroaromatic two major classes.In general, heteroaromatic Ring system has a degree of stability and armaticity, and in general chemical reaction, ring is not easily broken.Part heteroaromatic can gather Synthetic macromolecule resin has extensive potential using value due to its unique excellent performance.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of virtues of high transparency Heterocycle polymer resin, the aromatic heterocyclic polymer resin transparency with higher also have good dimensional stability, heat-resisting The performances such as property, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of preparation method of the aromatic heterocyclic polymer resin of high transparency, the systems Preparation Method step is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, can large-scale industry life It produces.
Another purpose of the invention is that providing a kind of application of the aromatic heterocyclic polymer resin of high transparency.
The purpose of the invention is achieved by the following technical solution: a kind of aromatic heterocyclic polymer resin of high transparency, the virtue The structural formula of heterocycle polymer resin is as follows:
Or
Or
Wherein, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is to replace Fluorine；M, n, x and y are positive integer.
Preferably, the aromatic heterocyclic polymer resin is modified using inorganic filler.
Preferably, the inorganic filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxygen At least one of compound, sulfate, carbonate, silicate, fluosilicate and phosphate.
Preferably, the nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；Institute Stating oxide is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
Preferably, the silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
Preferably, the sulfate be calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, in ferrous sulfate extremely Few one kind；The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, carbonic acid At least one of magnesium and zinc carbonate；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate； The phosphate is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
Preferably, the aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, crystalline substance At least one of the short fine, silicone of palpus, carbon fiber, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
Another object of the present invention is achieved through the following technical solutions: a kind of aromatic heterocyclic polymer resin of high transparency Preparation method is being sent out using at least one of fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid and hydrazine sulfate as reaction raw materials Polycondensation reaction is carried out in cigarette sulfuric acid, obtains the aromatic heterocyclic polymer resin.
Specifically, when using fluorine-containing terephthalic acid (TPA) as monomer, fluorine-containing terephthalic acid (TPA), hydrazine sulfate and oleum Molar ratio is 1:(1.01-5.0): (5-15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
When using fluorine-containing phthalic acid as monomer, the molar ratio of fluorine-containing phthalic acid, hydrazine sulfate and oleum For 1:(1.01-5.0): (5-15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
When using fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid as monomer, fluorine-containing terephthalic acid (TPA), fluorine-containing adjacent benzene The molar ratio of dioctyl phthalate, hydrazine sulfate and oleum is (0.01-0.99): (0.99-0.01): (1.01-5.0): (5-15), Middle oleum molal quantity is with SO in oleum3Molal quantity meter.When with fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid work When for monomer, polymerization methods have random copolymerization, alternating copolymerization or block copolymerization.
An also purpose of the invention is achieved through the following technical solutions: a kind of aromatic heterocyclic polymer resin of high transparency Using the aromatic heterocyclic polymer resin is applied to fiber or film.
Preferably, the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, stone Inkization heat dissipation film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand Cover plate.
The beneficial effects of the present invention are: aromatic heterocyclic polymer resin transparency with higher of the invention also has The property such as good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent Can, excellent combination property.
Preparation method step of the invention is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, It can large-scale industrial production.
The aromatic heterocyclic polymer resin of high transparency of the invention high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, Be carbonized film base material, graphitization heat dissipation film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, height The application of warm insulating film or hand-set lid.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of aromatic heterocyclic polymer resin of high transparency, the structural formula of the aromatic heterocyclic polymer resin are as follows:
Wherein, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is to replace Fluorine；M is positive integer.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is in mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide and oxide At least one.
The nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxidation Object is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
The silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
A kind of preparation method of the aromatic heterocyclic polymer resin of high transparency is reaction with fluorine-containing terephthalic acid (TPA) and hydrazine sulfate Raw material carries out polycondensation reaction in oleum, obtains the aromatic heterocyclic polymer resin.Fluorine-containing terephthalic acid (TPA), hydrazine sulfate Be 1:(1.01,2.0,3.0,4.0 or 5.0) with the molar ratio of oleum: (5,8,10,12 or 15), wherein oleum rubs That number is with SO in oleum3Molal quantity meter.
Embodiment 2
A kind of aromatic heterocyclic polymer resin of high transparency, the structural formula of the aromatic heterocyclic polymer resin are as follows:
Wherein, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is to replace Fluorine；N is positive integer.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is at least one of sulfate, carbonate, silicate, fluosilicate and phosphate.
The sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate； The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, magnesium carbonate and carbonic acid At least one of zinc；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphoric acid Salt is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
A kind of preparation method of the aromatic heterocyclic polymer resin of high transparency, at least one of fluorine-containing phthalic acid and Hydrazine sulfate is reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Fluorine-containing neighbour's benzene two The molar ratio of formic acid, hydrazine sulfate and oleum is for 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein Oleum molal quantity is with SO in oleum3Molal quantity meter.
Embodiment 3
A kind of aromatic heterocyclic polymer resin of high transparency, the structural formula of the aromatic heterocyclic polymer resin are as follows:
Wherein, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is to replace Fluorine；X and y is positive integer.
The aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber At least one of the short fine, silicone of dimension, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
A kind of preparation method of the aromatic heterocyclic polymer resin of high transparency, with fluorine-containing terephthalic acid (TPA), fluorine-containing O-phthalic Acid and hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.It is fluorine-containing right Phthalic acid, fluorine-containing phthalic acid, hydrazine sulfate and oleum molar ratio be (0.01,0.30,0.50,0.80 or 0.99): (0.99,0.80,0.50,0.30 or 0.01): (1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), Middle oleum molal quantity is with SO in oleum3Molal quantity meter.
Embodiment 4
A kind of application of the aromatic heterocyclic polymer resin of high transparency, the aromatic heterocyclic polymer resin are applied to fiber.
Embodiment 5
A kind of application of the aromatic heterocyclic polymer resin of high transparency, the aromatic heterocyclic polymer resin are applied to film.
The film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation Film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
After tested, it can achieve 91-95% using film clarity made from aromatic heterocyclic polymer resin of the invention, have There is higher transparency.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way, Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.

Claims (10)

1. a kind of aromatic heterocyclic polymer resin of high transparency, it is characterised in that: the structural formula of the aromatic heterocyclic polymer resin is such as Under:
Or
Or
Wherein, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is the fluorine replaced； M, n, x and y are positive integer.
2. a kind of aromatic heterocyclic polymer resin of high transparency according to claim 1, it is characterised in that: the heteroaromatic is poly- Polymer resin is modified using inorganic filler.
3. a kind of aromatic heterocyclic polymer resin of high transparency according to claim 2, it is characterised in that: the inorganic filler For mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfate, carbonate, silicate, fluorine At least one of silicate and phosphate.
4. a kind of aromatic heterocyclic polymer resin of high transparency according to claim 3, it is characterised in that: the nitride is Silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide is calcium oxide, zinc oxide, oxygen Change at least one of magnesium, iron oxide, silica and titanium dioxide.
5. a kind of aromatic heterocyclic polymer resin of high transparency according to claim 4, it is characterised in that: the silica For nano silica, the titanium dioxide is nano-titanium dioxide.
6. a kind of aromatic heterocyclic polymer resin of high transparency according to claim 3, it is characterised in that: the sulfate is At least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicate is sodium metasilicate, silicon At least one of sour aluminium and magnesium silicate；The carbonate is at least one of calcium carbonate, magnesium carbonate and zinc carbonate；The fluorine Silicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate be calcium phosphate, calcium monohydrogen phosphate, At least one of magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of aromatic heterocyclic polymer resin of high transparency according to claim 1, it is characterised in that: the heteroaromatic is poly- Polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber, glass fibre, aramid fiber slurry At least one of the short fine, silicone of the dregs of rice, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item preparation methods of the aromatic heterocyclic polymer resin of high transparency of claim 1-7, feature It is: using at least one of fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid and hydrazine sulfate as reaction raw materials, in oleum Polycondensation reaction is carried out in acid, obtains the aromatic heterocyclic polymer resin.
9. such as a kind of described in any item applications of the aromatic heterocyclic polymer resin of high transparency of claim 1-7, it is characterised in that: The aromatic heterocyclic polymer resin is applied to fiber or film.
10. a kind of application of the aromatic heterocyclic polymer resin of high transparency according to claim 9, it is characterised in that: described Film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation film base material, high temperature Protective film, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
CN201811145199.1A 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film Withdrawn CN109306180A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811145199.1A CN109306180A (en) 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811145199.1A CN109306180A (en) 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film

Publications (1)

Publication Number Publication Date
CN109306180A true CN109306180A (en) 2019-02-05

Family

ID=65225127

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811145199.1A Withdrawn CN109306180A (en) 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film

Country Status (1)

Country Link
CN (1) CN109306180A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979947A (en) * 2021-05-13 2021-06-18 北京拜欧泰克科技有限公司 Aromatic polyoxadiazole, aromatic polyoxadiazole film and preparation method of film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007133409A2 (en) * 2006-05-01 2007-11-22 E. I. Du Pont De Nemours And Company Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN101437871A (en) * 2006-05-01 2009-05-20 纳幕尔杜邦公司 Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN104093787A (en) * 2012-01-12 2014-10-08 韩华石油化学株式会社 Resin composition for emi shielding, comprising carbon hydride composite
CN104817687A (en) * 2015-05-22 2015-08-05 江苏宝德新材料有限公司 High-purity aromatic polyoxadiazole solution and fiber prepared from high-purity aromatic polyoxadiazole solution
CN104831400A (en) * 2015-05-22 2015-08-12 江苏宝德新材料有限公司 Low-viscosity aromatic polyoxdiazole solution and fiber prepared from same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007133409A2 (en) * 2006-05-01 2007-11-22 E. I. Du Pont De Nemours And Company Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN101437871A (en) * 2006-05-01 2009-05-20 纳幕尔杜邦公司 Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN104093787A (en) * 2012-01-12 2014-10-08 韩华石油化学株式会社 Resin composition for emi shielding, comprising carbon hydride composite
CN104817687A (en) * 2015-05-22 2015-08-05 江苏宝德新材料有限公司 High-purity aromatic polyoxadiazole solution and fiber prepared from high-purity aromatic polyoxadiazole solution
CN104831400A (en) * 2015-05-22 2015-08-12 江苏宝德新材料有限公司 Low-viscosity aromatic polyoxdiazole solution and fiber prepared from same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979947A (en) * 2021-05-13 2021-06-18 北京拜欧泰克科技有限公司 Aromatic polyoxadiazole, aromatic polyoxadiazole film and preparation method of film
WO2022237827A1 (en) * 2021-05-13 2022-11-17 陈瑾 Aromatic polyoxadiazole, and aromatic polyoxadiazole film and preparation method therefor

Similar Documents

Publication Publication Date Title
CN104530707A (en) Crystal whisker reinforced organic silicon heat conducting material and preparation method thereof
CN104530709A (en) Metal reinforced organic silicon heat conducting material and preparation method thereof
CN106496632A (en) A kind of preparation method of magnesium oxide Graphene composite heat-conducting insulating packing
CN109306180A (en) A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film
CN109280380A (en) A kind of aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant and preparation method thereof and application in fiber or film
CN109293893A (en) A kind of aromatic heterocyclic polymer resin of UV resistant high transparency and preparation method thereof and application in fiber or film
CN109293891A (en) A kind of aromatic heterocyclic polymer resin of high intensity and preparation method thereof and application in fiber or film
CN109401306A (en) A kind of aromatic heterocyclic polymer resin and preparation method thereof and application in fiber or film
JP2013166849A (en) Method of producing polysulfone composition and method of producing molded product
CN109293897A (en) A kind of aromatic heterocyclic polymer resin of high transparent and fire-retardant and preparation method thereof and application in fiber or film
CN109306183A (en) Fire-retardant aromatic heterocyclic polymer resin of a kind of high intensity UV resistant and preparation method thereof and application in fiber or film
US9879168B2 (en) Method for producing hexagonal boron nitride, and heat dissipation sheet
CN109320703A (en) A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and application in fiber or film
Haruki et al. Controlling thermal conductivities and electrical insulation properties of carbon nanofiber/polyimide composites using surface coating techniques
CN109293895A (en) A kind of fire-retardant aromatic heterocyclic polymer resin and preparation method thereof and application in fiber or film
CN109293894A (en) A kind of aromatic heterocyclic polymer film and its preparation method and application of high intensity UV resistant
CN109337048A (en) A kind of aromatic heterocyclic polymer resin and preparation method thereof of high intensity UV resistant and application in fiber or film
KR20200003609A (en) GRAPHITE FILM, preparing method thereof, and heat emission structure including the same
CN109306181A (en) A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and application in fiber or film
CN109401305A (en) A kind of aromatic heterocyclic polymer resin of UV resistant and preparation method thereof and application in fiber or film
CN109401307A (en) A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film
CN109320702A (en) A kind of aromatic heterocyclic polymer resin of high-strength and high-transparent and preparation method thereof and application in fiber or film
CN109337049A (en) A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparency and preparation method thereof and application in fiber or film
CN109337364A (en) A kind of aromatic heterocyclic polymer film of high intensity and its preparation method and application
CN109293898A (en) A kind of aromatic heterocyclic polymer resin of UV resistant high transparency and preparation method thereof and application in fiber or film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20190205